The use of objects molded from synthetic polymers has expanded rapidly in the last several decades. In particular, polyesters and polyamides have widely gained acceptance for general molding applications and in the formation of fibers and films. An additional class of polymers known as poly(ester-amides) has been disclosed. Such disclosures include U.S. Pat. Nos. 2,547,113; 2,946,769; 3,272,774; 3,272,776; 3,440,218; 3,475,385; 3,538,058; 3,546,178; 3,575,928; 3,676,291; 3,865,792; 3,926,923; and 4,116,943. Polyimide esters are disclosed in German Offenlegungsschrift No. 2,950,939 and in U.S. Pat. No. 4,176,223.
Although many polyesters, polyamides, and poly(ester-amides) have mechanical properties suitable for general applications, most polyesters, polyamides, and poly(ester-amdes) are not suitable for high strength service because the mechanical properties are not sufficiently high. One group of polymers that are suitable for high strength service without the use of a reinforcing agent is a new class of polymers exhibiting a general overall balance of mechanical properties substantially enhanced over previous polymers. These polymers and/or their melts have been described by various terms, including "liquid crystalline," "liquid crystal," "mesogenic," "thermotropic," and "anisotropic." Briefly, the polymers of this new class are thought to involve a parallel ordering of the molecular chains. The state wherein the molecules are so ordered is often referred to either as the liquid crystal state or the nematic phase of the liquid crystal state. These polymers are prepared from monomers which are generally long, flat, and fairly rigid along the long axis of the molecule and commonly have chain extending linkages that are either coaxial or parallel.
Disclosures of polyesters which exhibit melt anisotropy include (a) Polyester X7G-A Self-Reinforced Thermoplastic, by W. J. Jackson, Jr., H. F. Kuhfuss, and T. F. Gray, Jr., 30th Anniversary Technical Conference, 1975 Reinforced Plastics/ Composites Institute, The Society of the Plastics Industry, Inc., Section 17-D, Pages 1 to 4, (b) Belgian Pat. Nos. 828,935 and 828,936, (c) Dutch Pat. No. 7505551, (d) West German Nos. 2520819, 2520820, 2722120, 2834535, 28343536, and 2834537, (e) Japanese Nos. 43-223; 2132-116; 3017-692; and 3021-293, (f) U.S. Pat. Nos. 3,991,013; 3,991,014; 4,057,597; 4,066,620; 4,067,852; 4,075,262; 4,083,829; 4,093,595; 4,118,372; 4,130,545; 4,130,702; 4,146,702; 4,153,779; 4,156,070; 4,159,365; 4,161,470; 4,169,933; 4,181,792; 4,183,895; 4,184,996; 4,188,476; 4,201,856; 4,219,461; 4,224,433; 4,228,218; 4,230,817; 4,232,143; 4,232,144; 4,238,598; 4,238,599; 4,245,082; and 4,245,084; and (g) U.K. Application Nos. 2,002,404; 2,008,598A; and 2,030,158A. See also commonly assigned U.S. Ser. Nos. 54,049, filed July 2, 1979 (now U.S. Pat. No. 4,256,624); 91,003, filed Nov. 5, 1979 now U.S. Pat. No. 4,337,191; 109,573, filed Jan. 4, 1980 (now U.S. Pat. No. 4,265,802); 109,575, filed Jan. 4, 1980 (now U.S. Pat. No. 4,285,852) 128,759, filed Mar. 10, 1980 (now U.S. Pat. No. 4,299,756); 128,778, filed Mar. 10, 1980 (now U.S. Pat. No. 4,279,803, and 169,014, filed July 15, 1980 now U.S. Pat. No. 4,337,190.
Representative disclosures of liquid crystalline polyamide dopes include U.S. Pat. Nos. 3,673,143; 3,748,299; 3,767,756; 3,801,528; 3,804,791; 3,817,941; 3,819,587; 3,827,998; 3,836,498; 4,016,236; 4,018,735; 4,148,774; and Re. 30,352.
U.S. Pat. No. 4,182,842 discloses poly(ester-amides) prepared from an aromatic dicarboxylic acid, ethylene glycol, and a p-acylaminobenzoic acid. Such poly(ester-amides) are also disclosed in "Liquid Crystal Polymers. III. Preparation and Properties of Poly(Ester-Amides) from p-Aminobenzoic Acid and Poly(Ethylene Terephthalate)," by W. J. Jackson, Jr. and H. F. Kuhfuss, J. Appl. Polym. Sci., Vol. 25, No. 8, pp. 1685-94 (1980). A similar disclosure is Japan 54 125271. These references neither disclose nor suggest the poly(ester-amide) of the present invention.
European Patent Application No. 79301276.6 (Publication No. 0 007 715) discloses melt processable fiber-forming poly(ester-amides) comprising residues of one or more aminophenols selected from p-aminophenol and p-N-methylaminophenol and residues of one or more dicarboxylic acids. The poly(ester-amide) contains a balance of linear difunctional residues and dissymmetric difunctional residues derived from either the aminophenols or the acids. The linear difunctional residues and dissymmetric difunctional residues are chosen so as to give a produce which melts below its decomposition temperature and exhibits optical anisotropy in the melt. The patent neither discloses nor suggests the poly(ester-amide) of the present invention which contains a p-oxybenzoyl moiety.
U.S. Pat. No. 3,859,251 discloses a poly(ester-amide) which includes a dicarboxylic moiety which comprises 50 to 100 mole percent of units derived from an acyclic aliphatic dicarboxylic acid. Such units are not required in the poly(ester-amide) of the present invention. Moreover, there is no disclosure in the patent of the formation of an anisotropic melt phase.
U.S. Pat. No. 3,809,679 discloses poly(ester-amides) consisting of 10 to 90 mole percent of recurring structural units derived from a dicarboxylic acid dihalide and a dihydroxy compound of a specified formula and 10 to 90 mole percent of recurring structural units derived from a dicarboxylic acid dihyalide and a diamino compound of a specified formula. The poly(ester-amides) specifically exclude moieties derived from aromatic hydroxyacids, such as the p-oxybenzoyl moiety included in the poly(ester-amide) of the present invention. Furthermore, most, if not all, of the poly(ester-amides) disclosed are not readily melt processable, and there is no disclosure of the existence of an anisotropic melt phase.
Commonly assigned U.S. Application Ser. Nos. 214,557, filed December 9, 1980, entitled "Poly(ester-amide) Capable of Forming an Anisotropic Melt Phase Derived From 6-Hydroxy-2-Naphthoic Acid, Dicarboxylic Acid, and Aromatic Monomer Capable of Forming an Amide Linkage" (Inventors: Anthony J. East, Larry F. Charbonneau, and Gordon W. Calundann), Ser. No. 251,629, filed Apr. 6, 1981, entitled "Poly(ester-amide) Capable of Forming an Anistropic Melt Phase Derived From 6-Hydroxy-2-Naphthoic acid, Other Aromatic Hydroxyacid, Carbocyclic Dicarboxylic Acid, and Aromatic Monomer Capable of Forming an Amide Linkage" (Inventors: Larry F. Charbonneau, Anthony J. East, and Gordon W. Calundann), and Ser. No. 251,625, filed Apr. 6, 1981, entitled "Poly(ester-amide) Capable of Forming an Anisotropic Melt Phase Derived from 6-Hydroxy-2-Naphthoic Acid, Aromatic Monomer Capable of Forming an Amide Linkage, and Other Aromatic Hydroxyacid" (Inventors: Gordon W. Calundann, Larry F. Charbonneau, and Anthony J. East), disclose melt processable poly(ester-amides) exhibiting anisotropy in the melt phase which include an oxynaphthoyl moiety. The poly(ester-amide) of the present invention, which does not include an oxynaphthoyl moiety, likewise demonstrates anisotropy and excellent tractability in the melt phase.
Commonly assigned U.S. Application Ser. No. 251,818, filed Apr. 7, 1981, entitled "Poly(ester-amide) Capable of Forming an Anisotropic Melt Phase Derived from Dihydroxyanthraquinone, Hydroxybenzoic Acid, Dicarboxylic Acid, and Aromatic Monomer Capable of Forming an Amide Linkage" (Inventors: Larry F. Charbonneau, Gordon W. Calundann, and Anthony J. East), discloses a melt processable poly(ester-amide) exhibiting anisotropy in the melt phase which includes a 2,6-dioxyanthraquinone moiety in combination with other recited moieties. The poly(ester-amide) of the present invention, which does not include a 2,6-dioxyanthraquinone moiety, has been found to exhibit an anisotropic melt phase in combination with excellent tractability.
Therefore, it is an object of the present invention to provide an improved poly(ester-amide) which is suited for the formation of quality molded articles, melt extruded fibers, and melt extruded films.
It is also an object of the present invention to provide an improved poly(ester-amide) which forms a highly tractable melt phase.
It is also an object of the present invention to provide an improved poly(ester-amide) which forms an anisotropic melt phase at a temperature well below its decomposition temperature and which may form quality fibers, films, and molded articles.
it is also an object of the present invention to provide an improved melt processable poly(ester-amide) capable of forming an anisotropic melt phase at a temperature below approximately 400.degree. C., and preferably below approximately 350.degree. C.
It is also an object of the present invention to provide an improved melt processable poly(ester-amide) which exhibits improved adhesion, improved fatigue resistance, and increased transverse strength.
These and other objects, as well as the scope, nature, and utilization of the present invention, will be apparent to those skilled in the art from the following detailed description.